Process for breaking petroleum emulsions employing certain amine-modified thermoplastic phenol-aldehyde resins



. and the like.

No Drawing. Application August 24, 1953,

. Serial No. 376,240

Claims. (Cl. 252-344) Attention is directed to my co-pendingapplication,

. Serial No. 288,743, filed May 19, 1952, now abandoned.

:-: Said co-pending application relates to a process of condensingcertain phenol-aldehyde resins, therein described in detail, with abasic hydroxylated secondary monoamine, having not more than 32 carbonatoms in any group attached to the amino nitrogen atom, andformaldehyde.

Condensates obtained from phenol-aldehyde resins and alkanol amines areinvariably and inevitably oxyalkylation-susceptible by virtue of thepresence of at least some phenolic hydroxyls and presumably by thepresence of at least some alkanol radicals. Indeed, the most valuablederivatives of which I am aware are those obtained by the action ofmonoepoxides, such as ethylene oxide, propylene oxide, butylene oxide,glycide and methylglycide on the condensates herein described, in theratio of one to ten times the amount of oxide by weight of condensate.Such oxyalkylated derivatives are of outstanding value for theresolution of petroleum emulsions of the water-in-oil type.

As pointed out hereinafter, when prepared as herein described thecondensates may at times slowly lose formaldehyde when heated at themaximum reaction temperature for a considerable period of time. However,they are heat-stable in the usual sense of the word.

In the present instance, the proviso that the resinous condensationproduct resulting from the process be heatstable andoxyalkylation-susceptible is eliminated from the claims except itobviously characterizes an intermediate condensate. Note that suchqualification does characterize even the final product but is simplyomitted to avoid any possible conflict with what is said subsequently asto the elimination of formaldehyde.

Primarily, the products herein described are comparable to the productsdescribed in my aforementioned copending application, Serial No.288,743, insofar that they are organic solvent-soluble, i. e., dissolvein hydrocarbons or hydroxylated solvents, such as alcohols, particularlyhigher alcohols, in ethers, glycols, glycol ethers,

The characterization organic solventsoluble is intended to characterizethe materials as be ing soluble as differentiated from insoluble resins.However, in such instances when the ultimate condensation product isobtained by a two-step process and the first step results in anintermediate condensate such as that described in my eopendingapplication, Serial No. 288,743, I have employed the terminology of said.copending application, i. e., heat-stable and oxyalkylationsusceptibleto characterize the intermediate condensate, for the reason that, as faras I know, the intermediate type of condensate does not yieldformaldehyde on heating and thus is heat-stable.

The present invention is difierentiated from .said prior invention inthat although the same reactants are employed, instead of beingemployedwithin the ratio of 1:2:2 the ratio varies from 1:3:3 to 1:4:4 and evenup ill to 1:5 :5. This change in reactant ratio results in the formationof more complex and more complicated condensation products which, inturn, are more valuable, at

least ina number of cases, than the particular condensates described insaid aforementioned co-pending application, Serial ,No. 288,743.

As a matter of fact, condensates derived in the manner described in theabove mentioned co-pending application, Serial No. 288,743, may bereacted further with an additional amount of formaldehyde andhydroxylated secondary amine to produce the type of material hereinspecified, or if desired, the reactants may be combined in the ultimateproportion at the very beginning of the reaction; or, for that matter, asecond intermediate may be produced and this particular intermediatecombined with a product of the kind described in aforementioned SerialNo. 288,743.

Anyone of three methods of manufacture can be employed and all will bedescribed in greater detail subsequently. .My preference is to preparethe product as described in Serial No. 288,743 and then combine itadditionally with one to two moles of added secondary hydroxylated amineand at least an equimolar proportion of formaldehyde, based on the amineadded at the second stage.

Reference is again made to U. S. Patent No. 2,499,368 dated March 7,1950, to De Groote and Keiser. Attention ,is directed to that part ofthe text which appears in columns 28 and 29, lines 12 through 75, andlines 1 through 21, respectively. Reference is made to this .test withthe same force and effect as if it were herein included. This, inessence, means that the preferred product for resolution of petroleumemulsions of the water-inoil type is characterized by the fact that a-50 solution in xylene, or its equivalent, when mixed with one to threevolumes of water and shaken will produce an emulsion.

For purpose of convenience, what is said hereinafter will be dividedinto four parts:

Part 1 is concerned with the phenol-aldehyde resin which is subjected tomodification by condensation reaction to yield an amine-modified resin;

Part 2 is concerned with appropriate basic hydroxylated secondarymonoamines which may be employed in the preparation of the hereindescribed amine-modified resins;

Part 3 is concerned with reactions involving the resin, the amine, andformaldehyde to produce specific products or compounds;

Part 4 is concerned with uses for the products described in Part Three,preceding, for the resolution of petroleum emulsions.

PART 1 It is well known that one can readily purchase on the openmarket, or prepare, fusible, organic solvent-soluble, water-insolubleresin polymers of a composition approximated in an idealized form by theformula varies from 3 to 6, i. e., it varies from 1 to 4; R representsan aliphatic hydrocarbon substitutent, generally an alkyl & radicalhaving from 4 to 15 carbon atoms, such as a butyl, amul, hexyl, decyl ordodecyl radical. Where the divalent bridge radical is shown as beingderived from formaldehyde it may, of course, be derived from any otherreactive aldehyde having/8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it isnecessarily soluble in any organic solvent. This is particularly truewhere the resins are derived from trifunctional phenols as previouslynoted. However, even when obtained from a difunctional phenol, forinstance,

'paraphenylphenol, one may obtain a resin which is not soluble in anonoxygenated solvent, such as benzene, or xylene, but requires anoxygenated solvent such as a low molal alcohol, dioxane, ordiethyleneglycol diethylethere. Sometimes a mixture of the two solvents(oxygenated and nonoxygenated) will serve. See Example 9a of U. S.Patent No. 2,499,365, dated-March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in anonoxygenated solvent, such as benzene or xylene. This presents noproblem insofar that all that 'is required is to make a solubility teston commercially available resins, or else prepare resins which arexylene or benzenersoluble as described in aforementioned U. S.

Patent No. 2,499,365, or in U. S. Patent No. 2,499,368,

dated March 7, 1950, to De Groote and Keiserp In said patent there aredescribed oxyalkylation-susceptible, fusible, nonoxygenated-organicsolvent-soluble, Water insoluble, low-stage phenol-aldehyde resinshaving an average -molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule. These resins are difunctionalonly in regard to methylol-forming reactivity,

him: with the resin molecule, or even to a very slight extent, if atall, 2 resin units may combine without any product, as indicated in thefolloware derived by reaction between a difunctional monohydric phenoland an aldehyde having not over 8 carbon atoms and reactive toward saidphenol and are formed in the substantial absence of trifunctionalphenols. The phenol is of the formula in which R is an aliphatichydrocarbon radical having at least 4 carbon atoms and not more than 24carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously andreacted approximately one mole of the resin with two moles offormaldehyde and two moles of a basic nonhydroxylated secondary amine asspecified, following the same idealized over-simplification previouslyreferred to, the resultant product might be illustrated thThe basicnonhydroxylated amine may be designed RI HN In conducting reactions ofthis kind one does not necessarily obtain a hundred percent yield forobvious reasons. Certain side reactions may take place. For instance, 2moles of amine may combine with one mole of the aldehyde, or only onemole of the amine may c0mof manufacture.

particular aldehyde employed to form the resin.

amine in the reaction ing formulas:

H OH

As has been pointed out previously, as far as the resin unit goes onecan use a mole of aldehyde other than formaldehyde, such asacetaldehyde, propionaldehyde or butyraldehyde. The resin unit may beexemplified thus:

on I- on OH RII/, RIII in which R' is the divalent radical obtained fromthe For reasons which are obvious the condensation product obtainedappears to be described best in terms of the method As previously statedthe preparation of resins, the kind herein employed as reactants, isWell known. See previously mentioned U. S. Patent 2,499,368. Resins canbe made using an acid catalyst or basic catalyst or a catalyst havingneither acid nor basic properties in the ordinary sense or without anycatalyst at all. It is preferable that the resins employed besubstantially neutral. In other 'Words, if prepared by using a strongacid as a catalyst such strong acid should be neutralized. Similarly, ifa strong base is used as a catalyst it is preferable that the basebeneutralize'd although we have found that sometimes the reactiondescribed proceeded more rapidly in the presence of a small amount of afree base. The

' amount may be as small as a 200th of a percent and as increase incaustic sodaand caustic potash maybe used.

much as a few 10ths of a percent. Sometimes moderate H0wever,'the mostdesirable procedure in practically every 1 case is to have the resinneutral.

Inpreparingresins one does not get a single polymer,

i. e.,' one having just 3 units, or just'4 units, or just 5 units, orjust 6 units, etc. It is usually a mixture; for

instance, one approximating 4 phenolic nuclei will have some trimer andpentamer present. Thus, the molecular weight may be such that itcorresponds to a fractional value for n as, for example, 3.5, 4.5 or5.2.

In the actual manufacture off the resins we found no reason for usingother than those'which are lowest in price and most readily availablecommercially.

For purposes of convenience suitable resins are characterized in thefollowing table TABLE I M01. wt Ex. Position 3' of resin ample R of B.derived 1; molecule number from- (based on n+2) Formal- 3. 5 992. 5

dehyde. Tertiary butyl do. do 3. 5 882.5 Secondary butyl- 3. 5 882. 5Cyclohexyl P 8. 5 1, 025.5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3.5 S05 5 and tertiary amyl. Propyl 3. 5 805. 5 Tertiary hexyl 3. 5 1,036. 5 Octyl 3. 5 1, 190. 5 N onyl 3. 5 1, 267. 5 Decyl 3. 5 1, 344. 5Dodecyl 3. 5 1, 498. 5 Tertiary but 3. 5 945. 5

Tertiary amyl 3. 5 1. 022. 5 Nonyl dn do 3. 5 1, 330. 5 Tertiary bntyldo- Butyral- 3. 5 1,071. 5

dehyde Tertiary amyl do.. U. 3. 1, 148. 5 Nonyl d 3. 5 1, 456. 5Tertiary butyl 3. 5 1, 008. 5

Tertiary amy1 do 3. 5 1, 085. 5 Nonyl do 3. 5 1, 393. 5 Tertiary butylFormal- 4. 2 996. 6

dehyde Tertiary amyl do 4.2 1, 083. 4 Non dn 4. 2 1, 430. 6 Tertiarybutyl d0.-.. 0.- 4.8 1, 094.4 Tertiary amyl do .-do- 4. 8 1, 189. 6Nonyl fin d0 4. 8 1, 570. 4 Tertiary amyl 1. 5 604. 0 Cyclohexy do do 1.5 646. 0 Hexyl do 1. 5 653. 0 do do. Acetalde- 1. 5 688.0

hyde Octyl--- (in (in 1.5 786.0 Nonyl do .do 1. 5 835.0 Octyl flnButyral- 2. 0 986. 0

dehyde 35: 'Nony do 2.0 1, 028.0 4612 Amyl. rin (in 2. 0 850.0 37':Butyl. dn Formal- 2.0 636. 0

dehyde 38a Am do do 2.0 692.0 4011 Hexyl rln dn 2. 0 748. 0 40aCyclohexyL do do 2. 0 740. 0

PART 2 As has been pointed out previously the amine herein employed as areactant is a basic hydroxylated secondary monoamine whose compositionis indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radicalwhich may be heterocyclic in a few instances as in a secondary aminederived from furfurylamine by reaction as ethylene oxide or propyleneoxide. Furthermore, at least one of the radicals designed by R must haveat least one hydroxyl radical. A large number of secondary amines areavailable and may be suitably employed as reactants for the presentpurpose. Among others, one may employ diethanolamine, methylethanolamine, dipropanolamine and ethylpropanolamine. Other suitablesecondary amines are obtained, of course, by taking any suitable primaryamine, such as an alkylamine, an arylalkylamine, or an alicyclic amine,and trea ing the amine with one mole of an oxyalkylating agent, such asethylene oxide, propylene oxide, butylene oxide, glycide, ormethylglycide. Suitable primary amines which can be so converted intosecondary amines, include butylamine, amylamine, hexylamine, highermolecular weight amines derived from fatty acids, cyclohexylamine,benzylamine, furfurylamine, etc. In other instances secondary amineswhich have at least one hydroxyl radical can be treated similarly withan oxyalkylating agent, or, for that matter, with an alkylating agentsuch as benzylchloride, esters of chloroacetic acid, alkyl bromides,dimethylsulfate, esters or" sulfonic acid, etc., so as to convert theprimary amine into a secondary amine. Among others, such amines include2 amino 1 butanol, 2 amino 2 methyl 1 propanol, 2 amino 2 methyl- 1 3propanediol, 2 amino 2 ethyl 1,3 pr'opanediol. and tri(hydroxymethyl)aminomethane. Another example of such amines is illustrated by 4 amino 4methyl 2 pentanol.

Similarly, one can prepare suitable secondary amines which have not onlya hydroxyl group but also one or more divalent oxygen linkages as partof an ether radical. The preparation of such amines or suitablereactants for preparing them has been described in the literature andparticularly in two United States patents, to wit, U. S. Patents Nos.2,325,514, dated July 27, 1943, to Hester, and 2,355,337 dated August 8,1944, to Spence. The latter patent describes typical haloalkyl otherssuch as Such haloalkyl others can be reacted with ammonia or with aprimary amine, such as ethanolamine, propanolamine, monoglycerylamine,etc., to produce a secondary amine in which there is not only present ahydroxyl radical but a repetitious ether linkage. Compounds can bereadily obtained which are exemplified by the following formulas:

(CzH5O C2H4OC2H4) /NH HO 01H; (0:11:70 CIHAO CzH4O 02H) HOC2H4 (OAHDOCHzCHKCHs) 0 (CH3) CHCH2)\ /NH 11003114 (C1150 CH'ACHzO CHnCHBO OHECHI)\(CH3O CHzCHzCHaCHzCHaCHa) HO CgH4 or comparable compounds having twohydroxylated groups ot difierent lengths as in (H0 CHzCHzO CHzCHgOGHOHfl) HQCHaLCHaOH 11TH HO.CH2.0.CH2OH CH3 See, also, correspondinghydroxylated amines which can be obtained from rosin or similar rawmaterials and 15 described in U. S. Patent No. 2,510,063, dated June 6,

1950, to iBriefl Still other examples are illustrated by treatment ofcertain'secondaryamines, such as the following, with a mole of anoxyalkyla'ting agent as described; phenoxyethylamine,phenoxypropylamine, phenoxyalpha'methylethylamine, andphenoxypropylamine. v

Other procedures for production of suitable compounds having a hydroxylgroup and a single basic aminonitrogen atom can be obtained from anysuitable alcohol or the like by'reaction with a reagent which containsan epoxide group and a secondary amine group. Such reactants aredescribed, for example, in U. S. Patents Nos. 1,977,251 and 1,977,253,both dated October 16, 1934, to Stallmann. Among the reactants describedin said latter patent are the following:

oH2-oH-oH,-Nn-crn-(onoun-omen PART 3 The products obtained 'by theherein described processes represent cogeneric mixtures which are theresult of a condensation reaction or reactions. Since the resin moleculecannot be defined satisfactorily by formula, although it may be soillustrated in an idealized simplification, it is difficult to actuallydepict the final product of the cogeneric mixture except in terms of theprocess itself.

Previous reference has been made to the fact that the procedure hereinemployed is comparable, in a general way, to that which corresponds tosomewhat similar derivatives made either from phenols as differentiatedfrom a resin, or in the manufacture of a phenol-aminealdehyde resin; orelse from a particularly selected resin and an amine and formaldehyde inthe manner described in Bruson Patent No. 2,031,557 in order to obtain aheatreactive resin. Since the condensation products obtained are notheat-convertible and since manufacture is not restricted to a singlephase system, and since temperatures up to 150 C. or thereabouts may beemployed, it is obvious that the procedure becomes comparatively simple.Indeed, perhaps no descriptioun is necessary over and above what hasbeen said previously, in light of subsequent examples. However, forpurpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogenericmixtures is a resin pot of the kind described in aforementioned U. S.Patent No. 2,499,368. In most instances the resin selected is not apt tobe a fusible liquid at the early or low temperature stage of reaction ifemployed as subsequently described; in fact, usually it is apt to be asolid at distinctly higher temperatures, for instance, ordinary roomtemperature. Thus, we have found it convenient to use a solvent andparticularly one which can be removed readily at a comparativelymoderate temperature, for instance, at 150 C. A suitable solvent isusually benzene, xylene, or a comparable petroleum hydrocarbon or amixture of such or similar solvents. Indeed, resins which are notsoluble except in oxygenated solvents or mixtures containing suchsolvents are not here included as raw materials. The reaction can beconducted in such a way that the initial reaction, and perhaps the bulkof the reaction, takes place in a polychase system. However, ifdesirable, one can use an oxygenated solvent such as a low-boilingalcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcoholscan be used or one can use a comparatively non-volatile solvent such asdioxane or the diethylether or ethyleneglycol. One can also use amixture of benzene or xylene and such oxygenated solvents. Note thattheme of such oxygenated solvent is not required in the sense'thatitisnot necessary to use an initial resin which is soluble only in anoxygenated solvent 'as just.

' employed, which may be the commercial product which is approximately37%, or it may be diluted down to about 30% formaldehyde. However,paraformaldehyde can be used but it is more difiicult perhaps to add asolid material instead of the liquid solution and, everything else beingequal, the latter is apt to be more economical. In any event, water ispresent as water of reaction. If the solvent is completely removed atthe end of the process, no problem is involved if the material is usedfor any subsequent reaction. -However,if the reaction mass is going tobe subjected to some further reaction where the solvent may beobjectionable as in the case of ethyl or hexyl alcohol, and if there isto be subsequent oxyalkylation, then, obviously, the alcohols should notbe used or else it should be removed. The fact that an oxygenatedsolvent need not be employed, of course, is an advantage for reasonsstated.

Another factor, as far as the selection of solvent goes, is whether ornot the cogeneric mixture obtained at the end of the reaction is to beused as such or in the salt form. The cogeneric mixtures obtained areapt to be solids or thick viscous liquids in which there is some changefrom the initial resin itself, particularly if some of the initialsolvent is apt to remain without complete I removal. Even if one startswith a resin which is almost water-white in color, the products obtainedare almost invariably a dark red in color or at least a red-amber, orsome color which includes both an amber component and a reddishcomponent. By and large, the melting point is apt to be lower and theproducts may be more sticky and more tacky than the original resinitself. Depending on the resin selected and on the amine selected thecondensation product or reaction mass on a solvent-free basis may behard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants seflected, may bewater-insoluble, or water-dispersible, or water-soluble, or close tobeing water-soluble. Water solubility is enhanced, of course, by makinga solution in the acidified vehicle such as a dilute solution, forinstance, a 5% solution of hydrochloric acid, acetic acid, hydroxyaceticacid, etc. One also may convert the finished product into salts bysimply adding a stoichiometric amount of any selected acid and removingany water present by refluxing with benzene or the like. In fact, theselection. of the -solvent employed may depend in part whether or nottheproduct at the completion of the reaction is to be converted into a saltform.

In the next succeeding paragraph it is pointed out that frequenty it isconvenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum, if required. This applies, of course, only tothose circumstances Where it is desirable or necessary to remove thesolvent. Petroleum solvents, aromatic solvents, etc., can be used. Theselection of solvent, such as benzene, xylene, or the like, dependsprimarily on cost, i. e., the use of the most economical solvent andalso on three other factors, two of which have been previouslymentioned; (a) is the solvent to remain. in the reaction mass withoutremoval? (b) is thereaction mass to be subjected to further reaction Wevhave found no particular advantage in using a low temperature in theearly stage of the reaction because,

and for reasons explained, this is not necessary although it does applyin some other procedures that, in a general Way, bear some similarity tothe present procedure. There is no objection, of course, to giving thereaction an opportunity to proceed as far as it will at some lowtemperature, for instance 30 to 40 but ultimately one must employ thehigher temperature in order to obtain products of the kind hereindescribed. If a lower temperature react-ion is used initially the periodis not critical, in fact, it may be anything from a few hours up to 24hours. We have not found any case where it was necessary or evendesirable to hold the low temperature stage for more than 24 hours. Infact, we are not convinced there is any advantage in holding it at thisstage for more than 3 or 4 hours at the most. This, again, is a matterof convenience largely for one reason. In heating and stirring thereaction mass there is a tendency for formaldehyde to be lost. Thus, ifthe reaction can be conducted at a lower temperature, then the amount ofunreacted formaldehyde is decreased subsequently and makes it easier toprevent any loss. Here, again, this lower temperature is not necessaryby virtue of neat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products ofreaction are mutually soluble, then agitation is required only to theextent that it helps cooling or helps distribution of the incomingformaldehyde. This mutual solubility is not necessary as previouslypointed out but may be convenient under certain circumstances. On theother hand, if the products are not mug tualtly soluble then agitationshould be more vigorous for the reason that reaction probably takesplace principally at the interfaces and the more vigorous the agitationthe more interfacial area. The general procedure employed is invariablythe same when adding the resin and the selected solvent, such as benzeneor xylene. Refluxing should be long enough to insure that the resinadded, preferably in a powdered form, is completely soluble. However, ifthe resin is prepared as such it may be added in solution form, just aspreparation is described in aforementioned U. S. Patent 2,499,368. Afterthe resin is in complete solution the amine is added and stirred.Depending on the amine selected, it may or may not be soluble in theresin solution. If it is not soluble 1n the resin solution it may besoluble in the aqueous formaldehyde solution. If so, the resin then willdissolve in the formaldehyde solution as added, and if not, it 18 evenpossible that the initial reaction mass could be a three-phase systeminstead of a two-phase system although th s would be extremely unusual.This solution, or mechanical HllX- ture, if not completely soluble iscooled to at least the reaction temperature or somewhat below, forexample, 35 C. or slightly lower, provided this initial low temperaturestage is employed. The formaldehyde .15 then added in a suitable form.For reasons pointed out we prefer to use a solution and whether to use acommerical 37% concentration is simply a matter of choice. In largescale manufacturing there may be some advantage 1n using a 30% solutionof formaldehyde but apparently this is not true on a small laboratoryscale or pilot plant scale. 30% formaldehyde may tend to decrease anyformaldehyde loss or make it easier to control unreacted formaldehydeloss.

On a large scale if there is any difliculty with formaldehyde losscontrol, one can use a more dilute form of formaldehyde, for instance, a30% solution. The reaction can be conducted in an autoclave and noattempt made to remove water until the reaction is over. Generallyspeaking, such a procedure is'much less satisfactory for a number ofreasons. For example, the reaction does not seem to go to completion,foaming takes place, and other mechanical or chemical difiiculties areinvolved. We have found no advantage in using solid formaldehyde becauseeven here water of reaction is formed.

Returning again to the preferred method of reaction and particularlyfrom the standpoint of laboratory procedure employing a glass resin pot,when the reaction has proceeded as one can reasonably expect at a lowtemperature, for instance, after holding the reaction mass with orwithout stirring, depending on whether or not it is homogeneous, at 30or 40 C., for 4 or 5 hours, or at the most, up to 10-24 hours, we thencomplete the reaction by raising the temperature up to 150 C., orthereabouts a required. The initial low temperature proce dure can beeliminated or reduced to merely the shortest period of time which avoidsloss of amine or formaldehyde. At a higher temperature we use aphase-separating trap and subject the mixture to reflux condensationuntil the water of reaction and the water of solution of theformaldehyde is eliminated. We then permit the temperature to rise tosomewhere about C., and generally slightly above 100 C., and below C.,by eliminating the solvent or part of the solvent so the reaction massstays within this predetermined range. This period of heating andrefluxing, after the water is eliminated is continued until the reactionmass is homogeneous and then for one to three hours longer. The removalof the solvents is conducted in a conventional manner in the same way asthe removal of solvents in resin manufacture as described inaforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we haveinvariably employed approximately one mole of the resin based on themolecular weight of the resin molecule, 2 moles of the secondary amineand 2 moles of formaldehyde. In some instances we have added a trace ofcaustic as an added catalyst but have found no particular advantage inthis. In other cases we have used a slight excess of formaldehyde and,again, have not found any particular advantage in this. In other caseswe have used a slight excess of amine and, again, have not found anyparticular advantage in so doing. Whenever feasible we have checked thecompleteness of reaction in the usual ways, including the amount ofwater of reaction, molecular weight, and particularly in some instanceshave checked whether or not the end-product showed surfaceactivity,particularly in a dilute acetic acid solution. The nitrogen contentafter removal of unreacted amine, if any is present, is another index.

In light of What has been said previously, little more need be said asto the actual procedure employed for the preparation of the hereindescribed condensation products. The following example will serve by wayof illustration.

Example 1b The phenol-aldehyde resin is the one that has been identifiedpreviously as Example 2a. It was obtained from a para-tertiarybutylphenol and formaldehyde. The resin was prepared using an acidcatalyst which was completely neutralized at the end of the reaction.The molecular weight of the resin wa 882.5. This corresponded to anaverage of about 3 /2 phenolic nuclei, as the value for n which excludesthe 2 external nuclei, i. e., the resin was largely a mixture having 3nuclei and 4 nuclei, ex cluding the 2 external nuclei, or 5 and 6overall nuclei. Tlie resin so obtained in a neutral state had a lightamber co or.

882 grams of the resin identified as 2a preceding were powdered andmixed with 700 grams of xylene. The mixture was refluxed until solutionwas complete. It was then adjusted to approximately 30 to 35 C. and 210grams of diethanolamine added. The mixture was stirred vigorously andformaldehyde added slowly. The formaldehyde used was a 37% solution andgrams were employed which were added in about 3 hours. The mixture wasstirred vigorously and kept within a temperature range of 30 to 45 C.for about 21 hours. At

the end of this period of time it was refluxed, using a 1 lphase-separating trap and a small amount of aqueous distillate withdrawnfrom time to time and the presence of unreacted formaldehyde noted. Anyunreacted formaldehyde seemed to disappear within approximately 3 hours12 In other instances it has varied frcm approximately 24 to 36 hours.The time can be reduced by cutting the low temperature period to about 3to 6 hours.

Note that in Table II following there are a large numafter the refluxingwas started. As soon as the Odor of '5 her of added exampl sillustrating e same procedure. formaldehyde was no longer detectible thephase-separat- In each case the initial mixture was stirred and held att ing trap was set so as to eliminate all water of solution a fairly lowtemperature (30 to 40 C.) for a period of and reaction. After the waterwas eliminated part of ev r l h urs. Then r fl xing was employed untilthe the xylene Was removed until the temperature reached I" fformaldehyde ppe After e r f about 150 C. The mass was kept at thishigher tem- 10 formaldehyde disappeared the phase-separating trap wasperature for about 3% hours and reaction stopped. Duremployed toseparate out all the water both the solution ing this time anyadditional water, which'was probably and condensation. After all thewater had been separated water of reaction which had formed, waseliminated enough Xylene was taken out to have the final product i bymeans of the trap. The residual xylene was permitted reflux for severalhours somewhere in the range of 145 to stay in the cogeneric mixture. Asmall amount of 10 thfiroahollts- Usually the mlxtul'e Ylelded thesample was heated on a water bath to remove the a clear 80111121011 bythe time the bulk Of the water, 01 all excess xylene and the residualmaterial Was dark red in f he Wa r, had been removed. color and had theconsistency of a sticky fluid or a tacky Note that as pointed outpreviously, this procedure is a resin. The overall reaction time was alittle over 30 hours. illustrated by 24 examples in Table II.

TABLE II Strength of Reac- Reac- Max. Ex. Resin Amt, formal- Solventused tlon tion dis- No. used grs. Amine used and amount dehyde and amt.temp., time till.

soln. and O. (hrsj temp., amt. O.

882 Diethanolamine, 210 g .1 37%, 162 g... Xylene, 700 g. 32 137 480Diethanolamlne, 105 g 37%, 81 g. Xylene, 450 g 150 633 do d Xylene, 600g36 145 441 Dipropanolamine, 133 g 30%, 100 g Xylene, 400 g 34 146 480 dodo Xylene, 450 g 24 141 633 do a do Xylene, 600g. 24 145 882Ethylethanolamlne, 178 g 37%, 162 g Xylene, 700 g -26 24 152 480Ethylethanolamlne, 89 g 37%, 81 g Xylene, 450 g. 24-30 28 151 633 do dXylene, 600g 22-25 27 141 473 Cyclohexyl g Xylene, 450 g 21-31 146 511do. 31%, 81 g "Mao 22-23 36 its 665 do t cl0 Xylene, 650 g.... 20-24 27152 CzHsOC2H4OC2H4 13a--. 2a 441 NH, 176g "do Xylene, 400 g... 21-25 24150 HOCtHl CHHBO 021140 02114 1411--.. 5a 480 H, 176g -do..-.. Xylene,450g 207-26 26 146 HOO2H4 C H OCzH4OC2H4 V 15b 9a 595 NH, 176g.-do.-...- Xylene, 550 g..-. 21-27 30 147 HOOZHlOCzHAOCZHA 16b 2|z 441NH, 192g .d0.-..-. Xylene, 400 g..-- 20-22 30 148 HOOzH;

HOC2H4OC2H4OCzH4 1711--.. 6a 480 NH, 192;; --do --do 20-25 28 150 HOCgH;

HOCQH4OCH4OO2H4 18b. 14a 511 NH, 192g d0..-..-- Xylene, 500 g 21-24 V 32149 HOC3H4 HQC9H4OC2H4OC3H4 19b 22a 4923 NH,192g .d0 Xylene, 450 g....22-25 32 153 Boom CHz(OC2H4)a 20b 23a. 542 NH,206g 30%,100g-- Xylene,500g.... 21-23 36 151 OH;(OCzH4)a 210.. 25a... 54? NH,206g --do..- do25-30 34 14s noognr OHflOCzHOs 220.... 2a 441 NH, 206g do..... Xylene,40051.... 22-23 31 14s nocznt, I 2%--.. 2611-- a 59'sDecylethanolainlne, 201g 37%, 81 g Xylene, 500 g..-- 22-27 24 24b- 27a391 Deeylethanolamine, 100 g"; 30%, 5 gm- Xylene, 300 g.... 21-25 26 147As has been pointed out, what has been described previously is thecondensate implying the 1:2:2 ratio as specified in co-pendingapplication, Serial No. 288,743. Such material, which is the finalreaction of the aforementioned co-pending application, may be employedas an intermediate for the production of the herein described morecomplex condensates. Needless to say, such condensates can be obtainedwithout an intermediate step as noted previously and as will beillustrated subsequently. There has been a previous statement as to thepossible composition of the intermediate. Needless to say, the presentcondensates employing different reactant ratios, as for example, anincreased amount of the amine and an increased amount of formaldehyde,result in different ultimate products, at least in part.

Actually what resultants are obtained, or rather what cogeneric mixturesor resultants are obtained, is in part obscure. For purpose ofillustration a dialkanolamine, such as diethanolamine, will be used butit is to be noted that a monohydroxylated amine, for instance,ethylethanolamine, could be used. Consider the simple situation Where anintermediate amine condensate of the kind described and prepared in themanner specified previously, is reacted additionally with two moles ofdiethanolamine and two moles of formaldehyde, based on a mole of resinoriginally employed as a reactant in the intermediate manufacture.Obviously, one mole of formaldehyde could combine with two moles ofdiethanolamine, thus:

Furthermore, one mole of diethanolamine and one mole of formaldehydecould combine to form a cyclic compound, thus:

H H G2H4OH CCH /H EN H200 HO C2H2N C2H4OH -0 The compounds derived inthe above manner may then react with an aryl radical, or with theresidual amine radical in the intermediate. It has been suggested thatunder conditions as herein employed that reaction involves 2 phenolichydroxyl hydrogen atoms. Actually, the phenolic hydroxyl hydrogen atomsare part of the resin molecule but the reaction might be shown simplythus:

O CHzN CgHsOH R CZHAOH 14 Still another suggestion has been reactioninvolving the meta group in the terminal phenol radical. This can beindicated in the following manner:

Another suggestion has been that chemical reactivity takes place in thisparticular manner but instead of involving a hydrogen in the metaposition of a terminal phenol radical, there is involved instead ahydrogen atom which is part of a methylene bridge or the equivalent.This is not shown for the reason that it is comparable to the reactionpreviously suggested.

Still a different reaction has been suggested; that dehydration takesplace at terminal ethanol groups forming a terminal unsaturated linkageand thus ultimately entering into a vinyl condensation, or theequivalent.

Another thought is one which, in a general way, is perfectly reasonablebut any specific suggestion as to structure is obscure. The suggestionis of interest particularly since it may explain the elimination offormaldehyde in a subsequent stage of manufacture as referred to later.The idea briefly is nothing more than to the effect that formaldehydemay produce a divalent radical, thus:

1-1 which appears at some point between a nitrogen atom and a hydrogenatom, or between an oxygen atom and a hydrogen atom, or in some similarposition to give a compound which is only partially heat-stable at theupper temperature range.

See chapter 12, Formaldehyde, Walker, 2nd ed., 1953, Reinhold Pub.C0rp., N. Y.

Without attempting to explore the ultimate composition further it isobvious, in fact, that no further directions are really required for thereason that all one need do is employ the intermediates as described inTable II and add the designated amount of reactants and proceed aspreviously in approximately the same temperature range as before,generally speaking, to or C. Note, however, that if desired a differentamine can be used in the split-step procedure as, for example, one couldstart with dieth-anolamine and could complete the reaction in the secondstep by using diisopropanol-amine; or one could start withdiisopropanolamine and complete the second step by usingethylethanolamine; or one could start with dibutanolamine and completethe step using cyclohexanolamine. Furthermore, using the split stepprocedure, one can use an amine in which a phenyl group is directlyjoined to the amino nitrogen atom as in the case of phenylethanolamine,phenylpropanolarnine, phenylbutanolamine, etc. Furthermome, an acylradical may be part of the hydroxylated amine as, for example, acetylethanolarnine, oleyl propanolamine, cthanolstearylamine. Apparently ifthe basicity is high enough due to the inherent b asicity of theintermediate condensate, reaction will take place with amino compoundshaving hydroxyl groups and aminohydrogen atoms, even though in such casethe basicity is comparatively low due to the presence of a negativegroup, such as a phenyl group or acyl radical directly attached to theamino nitrogen atom. Oompounds may be employed having a sulfoinamidegroup present.

The procedure employed is illustrated by the following examples:

Example 10 The intermediate condensate employed was 1b. The particularsample represented a solution of approxi- 7 evolution during the mately1120 grams of the condensate and '700 grams of xylene.' To this therewere added 210 grams of diethanol amine and 162 grams of 37%formaldehyde; 'The mixture was stirred for approximately two hours atapproximately room temperature, for instance to C., and then refluxedfor 4 hours at a temperature in the neighborhood of the boiling point ofwater or somewhat higher. A phase-separating trap was then set toeliminate water of solution from aqueous formaldehyde and also water offormation and the temperature allowed to rise to approximately C. Duringthis stage some xylene was removed so as to allow the temperature torise to 150 C. or thereabouts and refluxing continued for a total of 6hours in this upper range, i. e., -160 C. In any event, refluxing wascontinued for at least 2 hours after" there was no further waterdraw-01f. At the end of this period lany xylene which had been distilledoff was returned to the mixture. In some instances some xylene or othersolvent was added, either at the start of the finish of the second step.This was purely a matter of convenience. Stirring was employedthroughout but at the end of the condensation step the entire mixturewas homogeneous and stirring was merely a matter of con venience forease of continuing the reaction and controlling even distillation. Thefinal condensate on a solvent-free basis was approximately 1400 grams.

As has been pointed out previously, for one mole of resin used initiallythere are employed at least three moles of formaldehyde and three molesof the hydroxylated secondary amine, i. e., at least One mole more offormaldehyde and at least one mole more of amine and specified as thebasis of reaction in the formula mentioned in co-pending application,Serial No. 288,743. As a matter of 'fact, our preferred ratio isapproximately 1:3.5:'3.5, or at the most 1:4:4. 1

Stated another way, if one starts with the intermediate condensate asdescribed in Table II, preceding, there is added a minimum of about 1.5moles amine and 1.5 moles present being evolved from a type of compoundwhich isstable at the low temperatures but not stable at the highertemperatures, for instance, 130, 140 or Finally,

there seems to be'a slow evolution of formaldehyde as long as theoperation is continued especially at the maximum temperature. If theformaldehyde forms a stable compound, or compounds, there seems to be abreak up at a slow rate in the final stages in most instances. Thissimply means the weight of the final product is generally less'than theweight would be if all the formaldehyde combined chemically. This isshown in the tabular data in Table 111. If there were a definite pointwhere evolution of formaldehyde ceased it might throw some light on thepossible structure of mixture of compounds obtained. There is no doubtthat in a number of instances where perhaps 3.5 or 4 moles offormaldehyde are empioyed the amount combined chemically at the end ofthe reaction period may not be in excess of event less than 3.

2.5 or in any This point is emphasized merely to the extent that it isan explanation of what appears in Table III.

In the table the value for the final product on a solventfree basis isdetermined by taking a small sample and evaporating in vacuum so astoeliminate the xylene.

No elTort was made to eliminate the xylene from the reaction mass forthe simple reason that it was most advantageous to keep it as asolution. The residual product was examined for color and there mighthave been a further loss of formaldehyde during this small-scaleevaporation stage. Furthermore, there might also be a trace of xyleneremaining behind. In other words, the final figures for the completedcondensate product are values which are as close as can be determinedfor reasonable accuracy but may be subject to some variation.

TABLE III Reaction Amt. of Interme- Amt. sol- Amt. 37% Added periodMaxifinal con- Complete diate convent free Solvent Amine formalsolvent;Reflux after mum disdensate condensate, densate, basis, (xylene),Secondary amine compound CODJ- dehyde, if an period water tillation(solvent- Ex. No. EX. N 0. grams grams pound, grams (xylene), (hrs.)take-01f mp., free grams grams (hrs.) 0. basis), grams 1, 120 700Diethanolamine 210 6 2 160 1, 420 1, 230 1, 000 do 210 6 2 1, 530 1, 515 210 5 3 153 1,800 1, 165 900 265 5. 5 2. 5 162 1, 440 1, 275 265 5 2.75 145 1, 550 1, 590 265 6 3 147 1, 865 1, 120 265 7 3 155 1, 400 1, 230265 7 4 157 1, 500 1, 165 210 6 2 160 1, 395 1, 275 210 4. 76 2 163 1,590 1, 120 157 5 2% 160 1, 350 1, 230 157 5 3 162 1, 445 1, 160 200 6 3154 1, 430 1, 28 0 200 6 3 151 1, 465

more formaldehyde and in some cases 2 moles more of Example 1d each one,than in the preparation of condensates of the kind described in myaforementioned application, Serial No. 288,743.

The reaction, regardless of how conducted, that is, whether it goesthrough an intermediate condensation or not, is continued until there isno more evolution of water and for some time beyond, for instance, oneor two hours. During this last stage there is usually a continuedevolution of formaldehyde. In the early stages, formaldehyde that isevolved is unquestionably uncornbined formaldehyde which is not solublein the reaction mass or at least formaldehyde..which is'evolved duringthe stage that the reaction mass is not homogeneous. Secondly, thereseems to be a continuation of formaldehyde stage where the reaction massis This is merely an example illustrating the procedure employed whichis identical with that .used in the manufacture of Example 1b but inwhich the amount of reactants employed at the very start are identicalwith those employed in both steps of 10. Stated another way, as far asone can determine, the ultimate composition of 1b is the same as that of1c. The resin used was phenolaldehyde resin 2a, and the amount used was882 grams. The amount of xylene used was 800 grams and the amount ofdiethanolamine was just twice that used in Example 1b, to wit, 420grams, and the amount of formaldehyde (37% solution) was just twice thatused in Example 15, to wit, 324 grams. The various time periods weresubstantially the same as in 1b, and the temperatures at various stagesthe same as in 1b. The product obtained at the end of the reaction, forall practical purposes, seemed to be the same as in 1c. The yield wassubstantially the same as the yield of 10, to wit, 1415 grams on asolvent-free basis.

Example 1e This is simply a further alternate procedure which can beemployed. The procedure which can be employed. The procedure is the sameas in 10, to wit, the same amount of intermediate condensate 1b isemployed, to wit, 1120 grams on a solvent-free basis. 600 grams ofsolvent were used. However, the additional amine employed, andformaldehyde employed, were reacted separately and then added tointermediate resin 1b. 210 grams of diethanolamine were reacted with 162grams of 37% formaldehyde in a separate vessel by simply stirring atroom temperature (20 to 35 C.) for six hours. The next step consisted inrefluxing for 2 hours. Prior to the reflux stage 200 grams of xylenewere added. After 2 hours refluxing a phase-separating trap was employedto start the elimination of water. During this stage not only was watereliminated but also uncombined formaldehyde. After the water wasentirely eliminated, some solvent was removed until the temperature roseto about the range of 145 to 155 C. The reaction was continued at thistemperature for about 3 /2 hours more. The mass was then transferred andmixed with the intermediate 1b, previously described (1120 grams ofintermediate condensate and 700 grams of xylene) in another vessel. 162grams of formaldehyde (37% solution) were added and from this pointforward the reaction was handled in the same manner as 10. The finalproduct appeared to be identical, as far as physical appearance goes,with or lb.

Previous reference has been made to the color of intermediate 1b.Actually, color and consistency of all the products prepared are muchthe same, to wit, varying from red to red-amber to dark red or almostblackish red. In each case the product obtained was softer than theoriginal resin, in fact, represented either a semi-viscous or viscousliquid. In some instances the viscosity of the liquid was extremelyhigh. Actually, there is no advantage in decolorization particularly forthe purpose herein described. If desired, the product could bedecolorized by using filtering clays, chars, or the like, in the samemanner as noted in connection with 1b.

PART 4 As to the use of conventional demulsifying agents, reference ismade to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote,and particularly to Part 3. Everything that appears therein applies withequal force and effect to the instant process, noting only that Wherereference is made to Example 13b in said text beginning in column 15 andending in column 18, reference should be to Example 56, hereindescribed.

Having thus described my invention, what I claim as new and desire tosecure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifier;said demulsifier being the product obtained by the process of condensing(a) an oxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol, said resinbeing formed 18 in the substantial absence of trifunctional phenols;said phenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2, 4, 6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (c) formaldehyde; said condensationreaction being conducted at a temperature sufiiciently high to eliminatewater and below the pyrolytic point of the reactants and resultants ofreaction; with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in which each ofthe three reactantsv have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resin molecule; with the further proviso that theratio of reactants be approximately 1:3:3 to 1:4:4, respectively, andwith the final proviso that the resinous condensation product resultingfrom the process be organic solvent-soluble.

2. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifier;said demulsifier being the product obtained by the process of condensing(a) an oxyalkylation-susceptible, fusible, nonoxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (0) formaldehyde; said condensationreaction being conducted at a temperature sufficiently high to eliminatewater and below the pyrolytic point of the reactants and resultants ofreaction; with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultants in which eachof the three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resinmolecule; with the further proviso that theratio of reactants be approximately 1:3:3 to 1:4:4, respectively; withthe added proviso that the ratio of hydroxylated secondary monoamine tothe resin molecule and the ratio of formaldehyde to the resin molecule,be identical; and with the final proviso that the resinous condensationproduct resulting from the process be organic solvent-soluble.

3. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifier;said demulsifier being the product obtained by a two-step condensationprocess involving (A) the process of condensing (a) anoxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight correin which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and formaldehyde; said condensation reactionbeing conducted at a temperature sufiiciently high to eliminate waterand below the pyrolytic point of the reactants and resultants ofreaction; with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in which each ofthe three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resin molecule; with the further proviso that theratio of reactants be approximately 1,2 and 2 respectively; and with theadded proviso that the resinous condensation product resulting from theprocess be heat-stable and oxyalkylation-susceptible; followed by (B) asecond step in which there is introduced additionally l to 2 moles of ahydroxylated monoamine and 1 to 2 moles of formaldehyde calculated onthe basis of the original resin molecule to the aforementionedcondensate intermediate and then resuming condensation until reactionceases, and with the final proviso that the product of reaction beorganic solvent-soluble.

4. The emulsion breaking process of claim 3 in which in the preparationof the demulsifier by the condensation process the amine used in thesecond step is the same amine as the one used in the first step.

5. The emulsion breaking process of claim 3 in which in the preparationof the demulsifier by the condensation process the amine used in thesecond step is the same amine as the one used in the first step and theratio of hydroxylated secondary amine to intermediate condensate andratio of formaldehyde to intermediate condensate is identical.

6. The emulsion breaking process of claim 3 in which in the preparationof the demulsifier by thecondensation process the amine used in thesecond step is the same amine as the one used in the first step and theratio of hydroxylated secondary amine to intermediate condensate is 1.5to l, and the ratio of formaldehyde to intermediate condensate is 1.5 to1.

7. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion 20 to the action of ademulsifier; said demulsifier being the product obtained by a-two-stepcondensation process in volving (A) the process" of condensing f(a)iahoxyalkyla' tion-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having anaverage molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylolforming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula i in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a dialkanolamine, and (0)formaldehyde; said condensation reaction being conducted at atemperature sufiiciently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction; with the proviso thatthe condensation reaction be conducted so as to produce a-significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of aformaldehyde-derived methylene bridge connecting the amino nitrogen atomwith a resin molecule; with the further proviso that the ratio ofreactants be approximately 1,2 and 2 respectively; and with the addedproviso that the resinous condensation product resulting from theprocess be heat-stable and oxyalkylation-susceptible, followed'by (B) asecond step in which there is introduced additionally 1.5 moles of thesame dialkanolamine used in the first condensation step, and 1.5 molesof formaldehyd'e, followed by resumption of condensation until reactionceases, and with the final proviso that the product of reaction beorganic solvent-soluble. '8. The emulsion breaking process of claim 7 inwhich in the preparation of the demulsifier by the condensation processthe dialkanolamine is 'diethanolamine.

9. The emulsion breaking process'of claim 7 in which in the preparationof the demulsifier by the condensation process the dialkanolamine isdipropylamine;

10. The emulsion breaking process of claim 7 in which in the preparationof the demulsifier by the condensation process the dialkanolamine isdibutanolamine.

References Cited in the file of this patent UNITED STATES PATENTS2,098,869 Harmon et a1. Nov. 9, 1937 2,191,943 Russell et a1 Feb. 27,1940 2,457,634 Bond et a1. Dec. 28, 1948 2,589,198 Monson Mar. 11, 19522,679,484 De Groote May 25, 1954 2,679,485 De Groote May 25, 1954

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER;SAID DEMULSIFIER BEING THE PRODUCT OBTAINED BY THE PROCESS OF CONDENSING(A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANICSOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVINGAN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLYIN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL, SAID RESINBEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAIDPHENOL BEING OF THE FORMULA